WO2012124740A1 - Polyamide et composition de polyamide - Google Patents

Polyamide et composition de polyamide Download PDF

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Publication number
WO2012124740A1
WO2012124740A1 PCT/JP2012/056588 JP2012056588W WO2012124740A1 WO 2012124740 A1 WO2012124740 A1 WO 2012124740A1 JP 2012056588 W JP2012056588 W JP 2012056588W WO 2012124740 A1 WO2012124740 A1 WO 2012124740A1
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Prior art keywords
polyamide
acid
diamine
mol
dicarboxylic acid
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PCT/JP2012/056588
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English (en)
Japanese (ja)
Inventor
真次 家田
寺田　和範
祐 日戸
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旭化成ケミカルズ株式会社
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Application filed by 旭化成ケミカルズ株式会社 filed Critical 旭化成ケミカルズ株式会社
Priority to JP2013504758A priority Critical patent/JP5942229B2/ja
Priority to EP12758039.7A priority patent/EP2687555B1/fr
Priority to CN201280011151.6A priority patent/CN103403063B/zh
Priority to US14/001,043 priority patent/US9090739B2/en
Publication of WO2012124740A1 publication Critical patent/WO2012124740A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a polyamide and a polyamide composition.
  • Polyamides typified by polyamide 6 and polyamide 66 are excellent in molding processability, mechanical properties, and chemical resistance. It is widely used as various parts materials for automobiles, electric and electronic, industrial materials, daily use and household goods.
  • PA6 and PA66 have a low melting point and cannot satisfy these requirements in terms of heat resistance.
  • high melting point polyamides have been proposed.
  • PA6T a polyamide composed of terephthalic acid and hexamethylenediamine
  • PA6T is a high-melting-point polyamide having a melting point of about 370 ° C., it is difficult to obtain a molded product having sufficient characteristics due to severe pyrolysis of polyamide even if a molded product is obtained by melt molding.
  • PA6T is composed of an aliphatic polyamide such as PA6 and PA66, or an amorphous aromatic polyamide composed of isophthalic acid and hexamethylenediamine (hereinafter abbreviated as “PA6I”).
  • PA6I high melting point semi-aromatic polyamide
  • PA6T copolymer having terephthalic acid and hexamethylenediamine as main components, which have been melted to about 220-340 ° C. Is sometimes abbreviated as ")
  • Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as “a mixture of hexamethylene diamine and 2-methylpentamethylene diamine”, which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. May be abbreviated as “PA6T / 2MPDT”).
  • a high melting point aliphatic polyamide composed of adipic acid and tetramethylene diamine hereinafter sometimes abbreviated as “PA46”
  • PA46 a high melting point aliphatic polyamide composed of adipic acid and tetramethylene diamine
  • An alicyclic polyamide composed of a cyclic dicarboxylic acid and an aliphatic diamine has been proposed.
  • Patent Documents 2 and 3 disclose semi-fats of an alicyclic polyamide (hereinafter sometimes abbreviated as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and another polyamide.
  • a cyclic polyamide (hereinafter sometimes abbreviated as “PA6C copolymer”) is disclosed.
  • Patent Document 2 discloses that semi-alicyclic polyamide electrical and electronic members containing 1 to 40% 1,4-cyclohexanedicarboxylic acid as dicarboxylic acid units have improved solder heat resistance. Discloses that semi-alicyclic polyamide automobile parts are excellent in fluidity and toughness.
  • Patent Document 4 discloses that a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine has light resistance, toughness, moldability, lightness, And excellent heat resistance and the like. Further, as a method for producing the polyamide, 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine are reacted at 230 ° C. or lower to prepare a prepolymer, and the prepolymer is solid-phase polymerized at 230 ° C. to obtain a melting point of 311 ° C. Is disclosed.
  • Patent Document 5 discloses that a polyamide using 1,4-cyclohexanedicarboxylic acid having a trans / cis ratio of 50/50 to 97/3 as a raw material is excellent in heat resistance, low water absorption, light resistance, and the like. It is disclosed.
  • JP-T 6-503590 Japanese National Patent Publication No. 11-512476 JP 2001-514695 A Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 Pamphlet Japanese National Patent Publication No. 8-503018 JP 2003-292612 A JP 2004-75932 A JP 2010-1111843 A
  • the PA6T copolymer certainly has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it has low fluidity from the viewpoint of moldability and surface appearance characteristics of the molded product. Insufficient and further inferior toughness and light resistance. Therefore, when used as an exterior part, appearance characteristics are required, and when used for applications such as exposure to sunlight, improvement of those characteristics is required. Further, PA6T copolymer has a large specific gravity, and improvement in lightness is also desired.
  • PA6T / 2MPDT disclosed in Patent Document 1 can partially improve the problems of conventional PA6T copolymer, but fluidity, moldability, toughness, appearance of molded product surface, In terms of light resistance, the improvement level is insufficient.
  • the PA 46 has good heat resistance and moldability, but has a high water absorption rate, and there is a problem that a dimensional change due to water absorption and a decrease in mechanical properties are remarkably large. There are cases where it is not possible to meet the demands.
  • PA6C copolymers disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity. Furthermore, the polyamides disclosed in Patent Documents 4 and 5 are also insufficiently improved in terms of toughness, strength, and fluidity.
  • the problem to be solved by the present invention is to provide a polyamide composition excellent in heat resistance, heat stability, heat-resistant color tone stability, heat reflow resistance, and fogging properties, and a polyamide constituting the polyamide composition.
  • the polyamide of this embodiment is a polyamide obtained by polymerizing the following (a) and (b).
  • (A) A dicarboxylic acid containing at least 50 mol% of an alicyclic dicarboxylic acid.
  • (B) A diamine containing a diamine having a pentamethylenediamine skeleton of at least 50 mol%.
  • polyamide means a polymer having an amide bond (—NHCO—) in the main chain.
  • the polyamide of the present embodiment has a cyclic amino terminal, and the amount of the cyclic amino terminal is less than 30 ⁇ eq / g.
  • Examples of the substituent in the alicyclic dicarboxylic acid include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. Etc.
  • 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoint of heat resistance, low water absorption, strength, and the like.
  • A-1) One type of alicyclic dicarboxylic acid may be used alone, or two or more types may be used in combination.
  • Alicyclic dicarboxylic acids have trans and cis geometric isomers.
  • the alicyclic dicarboxylic acid as a raw material monomer for polyamide, either a trans isomer or a cis isomer may be used, or mixtures of various ratios of a trans isomer and a cis isomer may be used.
  • the alicyclic dicarboxylic acid is isomerized at a high temperature to have a certain ratio, and the cis isomer has higher water solubility of the equivalent salt with the diamine (b) described later than the trans isomer.
  • the raw material monomer has a trans isomer / cis isomer ratio of preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 35 in terms of molar ratio. / 65 to 15/85.
  • the trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).
  • aliphatic dicarboxylic acid examples include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, and 2,3-diethylglutaric acid.
  • aromatic dicarboxylic acid examples include unsubstituted or substituted terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid.
  • aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with various substituents.
  • the various substituents in the aromatic dicarboxylic acid include halogens such as alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, arylalkyl groups having 7 to 10 carbon atoms, chloro groups, and bromo groups.
  • Groups, silyl groups having 1 to 6 carbon atoms, and sulfonic acid groups and salts thereof such as sodium salts.
  • Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Of these, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance and the like.
  • A-2 One dicarboxylic acid other than the alicyclic dicarboxylic acid may be used alone, or two or more dicarboxylic acids may be used in combination.
  • dicarboxylic acid other than (a-2) alicyclic dicarboxylic acid in dicarboxylic acid contains aliphatic dicarboxylic acid having 10 or more carbon atoms
  • (a-1) alicyclic dicarboxylic acid is preferred.
  • the (b) diamine constituting the polyamide of this embodiment may be described as at least 50 mol% of a diamine having a pentamethylenediamine skeleton (hereinafter referred to as (b-1) a diamine having a pentamethylenediamine skeleton). )including.
  • (b) By using a diamine containing at least 50 mol% of a diamine having a pentamethylenediamine skeleton as the diamine, a polyamide that simultaneously satisfies strength, toughness and the like and has excellent moldability is obtained. be able to.
  • the diamine having a pentamethylenediamine skeleton can also be expressed as a diamine having a 1,5-diaminopentane skeleton.
  • Examples of the diamine having a pentamethylenediamine skeleton include pentamethylenediamine, 2-methylpentamethylenediamine, 2-ethylpentamethylenediamine, 3-n-butylpentamethylenediamine, 2,4-dimethylpentamethylenediamine, 2- Examples thereof include saturated aliphatic diamines having 5 to 20 carbon atoms such as methyl-3-ethylpentamethylenediamine and 2,2,4-trimethylpentamethylenediamine.
  • the diamine having a pentamethylenediamine skeleton is preferably pentamethylenediamine and 2-methylpentamethylenediamine, more preferably 2-methylpentamethylenediamine, from the viewpoints of heat resistance and strength. .
  • One type of diamine having a pentamethylenediamine skeleton may be used alone, or two or more types may be used in combination.
  • the addition amount (mol%) of lactam and / or aminocarboxylic acid is based on the molar amount of each monomer of (a) dicarboxylic acid, (b) diamine and (c) lactam and / or aminocarboxylic acid.
  • the content is preferably 0 to 20 mol%.
  • end-capping agent In the production process of the polyamide of the present embodiment, when polymerizing using the above-described (a) dicarboxylic acid and (b) diamine, and optionally (c) lactam and / or aminocarboxylic acid, for molecular weight adjustment.
  • the above-described known end-capping agent may be further added to carry out the polymerization.
  • an effective method includes a method of controlling the addition amount of diamine and terminal blocking agent as additives during hot melt polymerization of polyamide, and polymerization conditions.
  • the melting point of the polyamide of this embodiment is preferably 280 to 350 ° C. as Tm2 from the viewpoint of heat resistance.
  • the melting point of the polyamide can be controlled by the composition of the polyamide. Melting
  • the color tone of the polyamide of the present embodiment is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less as the b value.
  • the b value can be measured by the method described in the examples below. When the b value is 10 or less, a polyamide composition excellent in heat discoloration can be obtained.
  • Fibrous inorganic fillers such as glass fibers and carbon fibers are further used as sizing agents, copolymers and epoxy containing carboxylic anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers as constituent units.
  • Compounds, polyurethane resins, and homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts with primary, secondary, or tertiary amines thereof may be included.
  • the unsaturated vinyl monomer constituting the copolymer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer as structural units is not particularly limited, For example, styrene, ⁇ -methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate Styrene and butadiene are preferred.
  • polyamide composition as a heat stabilizer, phenol stabilizer, phosphorus stabilizer, amine stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table
  • phenol stabilizer, phosphorus stabilizer, amine stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table One or more selected from the group consisting of metal salts of Group IVb and Group IVb elements and halides of alkali metals and alkaline earth metals can be blended.
  • the metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table is not particularly limited and is preferably a heat stabilizer. Copper salt.
  • the copper salt is not particularly limited.
  • copper halide copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.
  • copper acetate copper propionate
  • benzoic acid examples thereof include copper oxide, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and copper complex salts in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid.
  • a mixture of a copper salt and a halide of alkali and alkaline earth metal can be suitably used as a heat stabilizer.
  • the ratio of the copper salt to the alkali and alkaline earth metal halide may be contained in the polyamide composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. It is preferably 5/1 to 30/1.
  • the molar ratio (halogen / copper) is within the above range, the heat aging resistance of the polyamide composition can be further improved.
  • the molar ratio (halogen / copper) is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed.
  • the molar ratio (halogen / copper) is 40/1 or less, corrosion of the screw or the like of the molding machine can be prevented without substantially impairing mechanical properties such as toughness.
  • the compounding amount of the inorganic filler is preferably 0.1 to 200 parts by mass, more preferably 1 to 180 parts by mass, and further preferably 5 to 150 parts by mass with respect to 100 parts by mass of the polyamide.
  • the blending amount is 0.1 parts by mass or more, the mechanical properties such as toughness, strength and rigidity of the polyamide composition are improved, and when the blending amount is 200 parts by mass or less, a polyamide having excellent moldability. A composition can be obtained.
  • the method for producing the polyamide composition when the inorganic filler contained in the polyamide composition is a reinforcing fiber having a weight average fiber length of 1 to 15 mm is not particularly limited.
  • the polyamide composition of this embodiment preferably has a sulfuric acid relative viscosity ⁇ r at 25 ° C. of 2.3 or more. More preferably, it is 2.3 to 7.0, still more preferably 2.5 to 5.5, and particularly preferably 2.8 to 4.0.
  • the relative viscosity ⁇ r of sulfuric acid at 25 ° C. is 2.3 or more, the mechanical properties such as toughness and strength are excellent.
  • the relative viscosity ⁇ r of sulfuric acid at 25 ° C. of the polyamide is preferably 7.0 or less.
  • the relative viscosity of sulfuric acid at 25 ° C. can be measured at 25 ° C.
  • the melting point Tm2 of the polyamide composition is preferably 280 to 350 ° C. from the viewpoint of heat resistance. Melting
  • polyamide and molded product of polyamide composition are known molding methods such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melt spinning. Etc. can be used to obtain various molded products.
  • the interior part is not particularly limited, and examples thereof include an instrument panel, a console box, a glove box, a steering wheel, and a trim.
  • the exterior parts are not particularly limited, and examples include a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, and a roof rail.
  • the electrical component is not particularly limited, and examples thereof include a connector, a wire harness connector, a motor component, a lamp socket, a sensor on-vehicle switch, and a combination switch.
  • the electric and electronic devices are not particularly limited, and are used for connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, motor end caps, and the like.
  • the industrial material is not particularly limited, and is used for gears, cams, insulating blocks, valves, electric tool parts, agricultural equipment parts, engine covers, and the like. It is not specifically limited as for daily use and household goods, for example, it is used for buttons, food containers, office furniture and the like. It does not specifically limit as an extrusion use, For example, it uses for a film, a sheet
  • the molar percentage of (a-1) alicyclic dicarboxylic acid is (number of moles of (a-1) alicyclic dicarboxylic acid added as raw material monomer / number of moles of all (a) dicarboxylic acid added as raw material monomer. ) ⁇ 100.
  • (B-1) mol% of diamine having pentamethylenediamine skeleton is ((b-1) moles of diamine having pentamethylenediamine skeleton added as raw material monomer / all (b) diamine added as raw material monomer The number of moles) was determined by calculation as 100. In the calculation by the above formula, the denominator and numerator do not include the number of moles of diamine having (b-1) pentamethylenediamine skeleton added as an additive during melt polymerization.
  • the endothermic peak temperature that appears on the highest temperature side of the endothermic peak (melting peak) that appears when the temperature is similarly raised at a temperature rate of 20 ° C./min is the melting point Tm2 (° C.), and the total peak area is the heat of fusion ⁇ H (J / g).
  • Tm2 melting point
  • J / g total peak area
  • Cyclic amino terminal amount ( ⁇ equivalent / g)> The cyclic amino terminal amount is 30 to 40 mg of polyamide dissolved in 1.2 g of hexafluoroisopropanol deuteride, and 1H-NMR (manufactured by JEOL Ltd., JNM ECA500) is used. Measured with Signal of hydrogen bonded to carbon adjacent to nitrogen atom of nitrogen heterocycle (chemical shift value 3.5-4.0 ppm) and signal of hydrogen bonded to carbon adjacent to nitrogen atom of amide bond of polyamide main chain ( The amount of cyclic amino terminus was calculated using an integration ratio of chemical shift values of 3.0 to 3.5 ppm.
  • the total amount of molecular chain end groups used at that time is GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (polymethyl methacrylate) standard sample (manufactured by Polymer Laboratories)) was calculated as 2 / Mn ⁇ 1,000,000 using the number average molecular weight (Mn) measured in (1).
  • GPC gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (polymethyl methacrylate) standard sample (manufactured by Polymer Laboratories)
  • ⁇ (5) ⁇ r retention rate during residence> When obtaining a multipurpose test piece (A type) from polyamide pellets, the test piece was injection molded by adjusting the cooling time so that the residence time in the screw was 6 minutes (average value). The ⁇ r of the test piece for 6 minutes of residence was measured by the method described in (2) above, and the relative value (100 fraction) when the ⁇ r of the polyamide pellet was taken as 100 was defined as the ⁇ r retention rate during residence.
  • Heat resistant color tone stability When obtaining a multipurpose test piece (A type) from polyamide pellets or polyamide composition pellets, test pieces having different residence times in the screw were prepared by adjusting the cooling time. Test pieces having an average residence time of 2 minutes, 6 minutes, and 10 minutes were prepared. The test piece having a residence time of 2 minutes was used as a reference sample, and a change in the color of the test piece due to the residence time was determined according to the following criteria. (Double-circle): Discoloration of a test piece is not recognized by retention for 10 minutes. ⁇ : Discoloration of the test piece is recognized by staying for 10 minutes. X: Discoloration of the test piece is recognized by staying for 6 minutes.
  • the hot-air reflow furnace used at this time is a lead-free solder compatible reflow furnace (UNI-6116H, manufactured by Nippon Antom Co., Ltd.).
  • the preheating zone temperature is 180 ° C.
  • the soldering zone temperature is 280. Set to ° C.
  • the conveyor belt speed in the reflow furnace was set to 0.3 m / min. Under this condition, the temperature profile in the furnace was confirmed.
  • the heat exposure time at 140 ° C. to 200 ° C. was 90 seconds, the heat exposure time at 220 ° C. or higher was 48 seconds, and the heat exposure time at 260 ° C. or higher was 11 seconds. There was a maximum temperature of 265 ° C.
  • the obtained multipurpose test piece (A type) was subjected to a tensile test at a tensile speed of 5 mm / min in accordance with ISO 527, and the tensile strength was measured.
  • the glass transition temperature Tg (° C.) was measured by using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121. Measurement conditions were such that a sample in a molten state obtained by melting a sample on a hot stage (EP80 manufactured by Mettler) was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the sample, the glass transition temperature was measured by raising the temperature in the range of 30 to 350 ° C. under the temperature raising speed of 20 ° C./min.
  • Example 1 Polymerization reaction of polyamide was carried out by “prepolymer / solid phase polymerization method”.
  • (A) CHDA 896 g (5.20 mol) and (b) 2MPD 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare a 50 mass% aqueous solution containing equimolar raw material monomers.
  • the obtained aqueous solution and 18 g (0.16 mol) of 2MPD, which is an additive at the time of polymerization, are charged into an autoclave (made by Nitto Koatsu) with an internal volume of 5.4 L, and kept warm until the liquid temperature (internal temperature) reaches 50 ° C. Then, the inside of the autoclave was replaced with nitrogen.
  • the pressure in the tank was reduced from 10 kg / cm 2 to atmospheric pressure (gauge pressure was 0 kg / cm 2 ) over 60 minutes. Furthermore, heating was continued, the heater temperature was adjusted so that the temperature in the autoclave became 220 ° C., and the reaction was performed for 3 hours while gradually removing the generated water vapor.
  • the obtained polyamide is pulverized to a size of 2 mm or less, dried in a nitrogen stream and adjusted so that the moisture content is less than about 0.2% by mass, and then the above measurements (1) to (10) are performed. It was. The measurement results are shown in Table 2.
  • Example 2 Using the polyamide obtained in [Example 1], “solid phase polymerization” was further carried out. 10 kg of the polyamide pellets obtained by the prepolymer / solid phase polymerization method were put into a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.), and sufficiently substituted with nitrogen. While flowing nitrogen at 1 L / min, heating was performed at 260 ° C. for 6 hours while stirring. Thereafter, the temperature was lowered while flowing nitrogen, and when the temperature reached about 50 ° C., the pellets were taken out from the apparatus to obtain polyamide. The obtained polyamides (1) to (10) were measured. The measurement results are shown in Table 2.
  • Example 3 As the (a) dicarboxylic acid, (b) diamine and additives during polymerization, the compounds and amounts shown in Table 1 below were used. In Example 4, acetic acid was used as a terminal blocking agent. The final temperature of the polymerization was set to the temperature shown in Table 1 below. For other conditions, the polyamide was polymerized by the prepolymer / solid phase polymerization method described in Example 1. Furthermore, the temperature and time described in Table 1 below were applied as the temperature and time for solid phase polymerization. The other conditions were the same as in Example 2 above, and solid phase polymerization was performed. The obtained polyamides (1) to (10) were measured. The measurement results are shown in Table 2.
  • the pressure in the tank was reduced from 30 kg / cm 2 to atmospheric pressure (gauge pressure was 0 kg / cm 2 ) over 60 minutes.
  • the heater temperature was adjusted so that the final temperature of the liquid temperature was 345 ° C.
  • the liquid temperature was maintained in that state for 10 minutes under a reduced pressure of 100 torr with a vacuum apparatus. Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain a polyamide.
  • the obtained polyamide was dried in a nitrogen stream and the moisture content was adjusted to be less than about 0.2% by mass, and then the above measurements (1) to (10) were performed.
  • the measurement results are shown in Table 2.
  • Comparative Example 2 In the said comparative example 1, it was set as the quantity of the following Table 1 as an quantity of the additive at the time of melt polymerization.
  • polyamide was polymerized by the hot melt polymerization method described in Comparative Example 1. Further, “solid phase polymerization” was carried out by the following method. 10 kg of the polyamide pellets obtained by melt polymerization were placed in a conical ribbon vacuum dryer (trade name ribocorn RM-10V, manufactured by Okawara Seisakusho Co., Ltd.) and sufficiently substituted with nitrogen. While flowing nitrogen at 1 L / min, heating was performed at 260 ° C. for 6 hours while stirring. Thereafter, the temperature was lowered while flowing nitrogen, and when the temperature reached about 50 ° C., the pellets were taken out from the apparatus to obtain polyamide. The obtained polyamides (1) to (10) were measured. The measurement results are shown in Table 2.
  • Glass fiber was supplied as a material in the ratio (parts by mass) shown in Table 3, and the melt-kneaded product extruded from the die head was cooled in a strand shape and pelletized to obtain a polyamide composition.
  • the measurement results of the above (7), (11), and (12) of the obtained polyamide composition are shown in Table 3 below.
  • the tensile speed in the tensile test was 5 mm / min.
  • Examples 8 to 14 The amounts of the raw material components were adjusted to the ratios shown in Table 3 below. Other conditions were the same as in the method described in Example 7 to obtain a polyamide composition. The measurement results of the above (7), (11), and (12) of the obtained polyamide composition are shown in Table 3 below. The tensile speed in the tensile test was 5 mm / min.
  • the polyamides of Examples 1 to 6 were excellent in all of heat resistance, heat stability, heat resistant color tone stability, heat reflow resistance, fogging property, and high melting point. It had the characteristics. Particularly, the polyamide of Example 4 satisfying 0.70 ⁇ total amount of molecular chain end groups ⁇ amino terminal amount ⁇ / total amount of molecular chain end groups ⁇ 1.00 had excellent characteristics. On the other hand, Comparative Examples 1, 2, and 3 having a cyclic amino terminal amount exceeding 30 ⁇ eq / g were insufficient in terms of heat-resistant color tone stability and fogging strength.
  • the polyamides of adipic acid and pentamethylenediamine of Comparative Examples 4 and 5 are excellent in heat-resistant color tone stability regardless of the cyclic amino terminal amount, and as in these Comparative Examples, polyamides having a low conventional processing temperature are used. Then, it became clear that there was no problem about the color stability at the time of processing. Furthermore, as is clear from the results in Table 3, the polyamide compositions of Examples 7 to 14 had excellent characteristics in terms of strength, heat-resistant color tone stability, and molding processability. On the other hand, the polyamide compositions of Comparative Examples 9 to 15 were insufficient in these respects.
  • the polyamide and the polyamide composition of the present invention have industrial applicability as molding materials for various parts such as automobiles, electric and electronic, industrial materials, and daily and household products.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a pour but de proposer une composition de polyamide qui présente une tolérance élevée à la chaleur, une stabilité élevée et une stabilité de couleur élevée lorsqu'elle est chauffée, une résistance élevée à une refusion thermique, et une performance élevée anti-buée. A cet effet, l'invention propose un polyamide obtenu par polymérisation : (a) d'acides dicarboxyliques, dont au moins 50 % en moles sont alicycliques ; et (b) de diamines, dont au moins 50 % ont des squelettes pentaméthylène diamine. Ledit polyamide contient des groupes terminaux amino cycliques dans une quantité inférieure à 30 µéq/g.
PCT/JP2012/056588 2011-03-15 2012-03-14 Polyamide et composition de polyamide WO2012124740A1 (fr)

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CN201280011151.6A CN103403063B (zh) 2011-03-15 2012-03-14 聚酰胺及聚酰胺组合物
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US20140039120A1 (en) 2014-02-06
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